Aroylaminonitrodiphenylamine



Patented Nov. 13, 1945 AnorLAMnvoNrrRonI'rHaNrLAMiNE Christopher StanleyArgyle, SpondonQnearDerhy,

England, assignor to British-Gelanese Limited, London, England, acompany -01 Great Britain 7 No Drawing. Application Novemberzfl itiflysbrial No. 466,324. In Great lZ ritain December 5, w

Claims. (01. etc-95 58 1 t f This invention relates to improvements inthe manufacture of dyes and in the colouration therewith of textile andother materials and particularly of materials containing fibres oforganic derivatives of cellulose, i. e. cellulose, esters of organiccarboxylic acids or cellulose others.

It has been found that valuable colourations,- particularly yellowcolourations, can be produced on textile and other materials, especiallymaterials of organic derivatives of cellulose, with th aid ofaroylamino-nitro-diarylamines.

The present invention includes the manufacture of the dyes, the dyesvthemselves, and compositions containing them together with othersubstances,-e. g. dispersing agents, processes for the colouration oftextileand other materials with'the dyes and the coloured materials soobtained.

The dyes of the invention possess excellent fastness propertiesand, in.particular, are veryresistant to steaming. They are, therefore, of

specialvalue for printing and broadly for application to material whichare subsequently to be subjected to-a steaming treatment; Ascomparedwith dyes of. similar constitution containing ac'etylamide instead of'aroylamino' groupsthey are of superior fastness to aqueous treatments.

By the term aroyl is meant an acidyl radicle containing an aryl radicle.'Ifhus the aroyl radicle canbe aracyl, e. .g'. benzoyl, or aralkacyl, e.g. phenylacetyl. 'Ihearoylamino group can be an aroylated primary aminogroup e. g.'benz 0ylamino-, or an "aroylated secondary amino group, e.g. benzoylmethylamino or other aroyl-alkylamino group. Advantageouslythe nitro group Speci'aHy noteworthy are 'thedyes of the.generalformula:

O NHQAJHQ where X represents a direct linkage between nucleus Aand the*CO- group, or is a CH2-- group, and the benzenenuclei may carry alkyl,halogen or alkoxy substituents.

Examples of dyes in accordance with the invention are2-,nitro-4-benzoylaminodiphenylamine, .4-chlor-.2-.nitro-4'-benzoylamino-diphenylamine", 2-nitro-4-benzoylamino-diphenylamine,Z-nitro 31 methyl- 4 benzoylaminodiphenyl amine, N- (2 nitro 4benzoylaminophenyl) -lnaphthylamineand the analogues of these compoundswherein the-benzoyl radicle i replaced by m-chlorbenzoyl-gp-methylbenzoyl p-methoxy benzoylor phenylacetyl.

The dyes of the invention are obtainable by aroylating an appropriateaminonitrodiarylamine with, for instance, the appropriate acid chlorideor anhydride. For example, 2-nitro-4-amino diphenylamine may bereactedwith benzoyl chloride or-with phenyl-acetyl chloride. Again, an

' appropriate aroylamino-diarylamine may be niand the acidylamino groupare present in'drfi'erent aromatic nuclei. Again it is. of advantagethat each or the aromatic nuclei in the dyes should'contain a singlebenzene ring and that the nitro group should be in the ortho-position tothe amino group, i. e. ortho to the amino group which unites the arylnuclei. The dyes may con taln other substituents, e. g. 'cyano, halogen,alkyl, alkoxy, oxyalkyl, oxyalkoxy, alkylsulphone, sulphonamide,arylamine, carboxylic amide, carboxylic ester or additional nitrogroups. Furtheremore, the amino group which unites the two aryl radiclesmay be substituted by, for example, a lower alkyl group. Preferablysulphonic acid and carboxylic acid group are absent from the dyes,

trated' although this method is not generally so convenient.

An alternative procedure for the preparation of the dyes or theinventioninvolves the condensation of two appropriately substituted aromaticcomponents. For example, a primary arylamine or a monoaryl-monoalkylsecondary amine can be condensed with an aryl compound carryin asasubstituent in an aryl nucleus, an atom'or group (e. g. a reactivehalogen atom, hydroxyl group, or nitro group) capable of reacting withthe primary or secondary amino group of the firstmentioned comp und withproduction ofa diarylamine or a diaryl-alkyl-amine asthe case maybe. Insuch cases one at least ofthe-qomponentsmust contain an aroylamino groupand one' at 'least of thecomponents must contain a nitro group. Thus anappropriate aryl halide may be condensed with an appropriate arylamine,and particularly an o-chlor-nitrobenzene with amonoaroylated-p-phenylene-diamine; e. g. o-chlornitrobenzene can bereacted with monobenzoyl-p-phenylenediamine to produce the2-nitrc-4'-benzoylaminodiphenylamine.

{Ifhe new dyes can be applied to cellulose ester Those dyes of thepresent invention which are;

free from sulpho and carboxy groups have sub-- stantive affinity forcellulose esters or-ethers but in general substantially no aiiinity forcellulose or animal fibres. If, thereforefsucha dyei'sf EXAMPL! IIPreparation of 2-m'tro-4'-(phenylacetylamilno) diphenylamine The abovecompound is prepared by condensing phenyl acetyl chloride (from phenylacetic acid and thionyl chloride) and 2-nitr0-4-aminodiphenylamine,conveniently prepared by acid hydrolysis of the corresponding acetylcomp nd-v 230. partsv by weight of 2-nitro-4 -amino-diphenylamine'are'dissolved in 1250 parts of benzene and 155 parts of phenyl acetylchloride added. The whole is refluxed for 6 hrs. and then allowed tocrystallise. The product is filtered oil and dried. Dyed on to celluloseacetate it gives goldenjyellow shades of good fastness to applied tomixed materials containing both eel-I lulose, e. g. cotton orregenerated cellulose, and a cellulose ester or ether, the latter alonetakes material remains uncoloured. By suitably colouring the cellulosecomponent of suchmixedn 1;

material with dyestufis resisting the cellulose ester or ether componentof "the materials, solid shades or two colour effects can readily beobtained according to the components and dyes selected. The dyestuff forthe cellulose portion can be applied before or after the application ofthe dye for thecellulose ester .or. etherportiom. The new dyes are alsoof value for colouring cellulose ester or ether solutions, especiallylacquers and spinning solutions. By shaping and setting such coloured.solutions in the form of fibres, straws, films and the..like,.valuablecol-. oured products can be produced. For example, coloured celluloseacetate filaments can bemoduced by dry spinning suchcoloured solutions.The invention,.so far as it relates .to the..col-. ouration ofmaterials, is particularlyconcerned withthe production;of,c0l0uredcellulose acetate products. The new dyes may, however, beused for theproduction of coloured Products of; other cellulose esters, for examplecellulose formate, propionate, butyrate or vacetate-butyrate, or ofcellulose ethers, for. example-methyl, ethyl .or benzyl cellulose.Further,.they.can beused for the colouring of materials formed from syn?thetic. linear. p lymers, e. .-superpolyamide tex-. tile materials. QThe following examples. illustrate. the, inven:

tion: I I

EXAMPLEI I Preparation of 2-nitro-4'-benzoylamino di I phenylamine M I Awell stirred mixture of 40 parts of orthonitroup the dye and thecellulose component of the" W sh a d. l ght" EXAMPLE III ApplicationIbr. .z-nitro-el-benzoylamino-diphenylamineto cellulose acetate ,10parts of a finely milled aqueous paste of 2-nitro-4benzoylamino-diphenylamine of 10% strength'are dispersed in the normalmanner by heating with 3 *parts of Turkeylred' oil 'anjd diluting withboi1ing 0.2 5% soap solution, and then adding to a dyebath containing 4000parts of 0;25-gm:p.-l.soapsolutionq "f" 100- parts of celluloseacetate fabric arenow introduced and the temperature raised I to 70- 809Gfat-whi'ch temperature-the material is proca essed'for l /z hrs. Thegoods'are'then washed ofi, hydroextracted anddried. The;shad'"thusobtained is a bright golden yellow 0 excellent fastness to light andlaunderingrfl Having" described'my invention what I desiretosecure'bylZ-ettersPatent-isi 7 ---1,'An 'aroylamino-ortho nitrodiizwhenylarnine of which the-aroyl radicle isselectedrfrom the groupconsisting of-"radicles of the formula CsH X-CO, wherein X represents alinkage'.se-' lected from the group-consisting of' the direct linkageand""-'CH2, and the nuclear'substitution r from the chlorbenzene, 100parts of monobenzoylparaphenylene diamine'and 20 parts of sodaash areheated in an oil bath at l50160 C. for 40 hours. After cooling, the meltis poured into 1000parts of boiling methylated spirits and precipitatedby pouring into 2000 parts of water at-70-80 C-rwith products ofradicles or said formula wherein the nuclear substituents' areselectedfrom "the group consisting'of 'allrylfhaloge'n and all'roxy. j"2." A aroylamino-nitro-diarylamine selected group consisting oficompoundsof the formula? W X e sen .e'. i k e. sel t rpiir h grove e n sins. o the. d ect .flli ls gfl. and a d t e nu lea su st tution-.prml tso'fjCbi'nbbnndS of the, said iormula wherein the said nuclearsubstituents" are selectedi irom the stirring. The dyestufi is filteredoif and washed Q group consisting of alkyl', halogen. and alkoxy.

3. 2 -nitifd-4'-bnzoylaliilnddipheliylalfiln. 4.. a em a- "5(phenylacetylaininoi idiphenyle a n I 5. 4-chlor-2 nitro-4=benzoylaminofdiphenylm fi I CHRISTOPHER STANLEY CERTIFICATE OF CORRECTION.

Patent No. 2,588,665.. November 1 191 CHRISTOPHER STANLEY ARGYLE.

It is hereby certified that error appears in the printed p cification ofthe above numbered patent requiring Correction as follows: Page 1, firstcolumn, line 26, for acetylamide read acetylamino--; and second column,line lLL, for methyl-LL" read -methylh'--; and that the said LettersPatent should be read with this correction therein that the same mayconform to the record of the case in the Patent Officec Signed andsealed this 29th day of January, A 1).. 19M),

Leslie Frazer (Seal)f' First Assistant Commissioner of Patents.

